Curriculum Map

Polymer Chemistry

Author: Eric M. Todd, Assistant Professor, University of Wisconsin–Stevens Point, Stevens Point, Wisconsin

Course Topics

Polymer Structure (Morphology and Molecular Weight)
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Article Section This brief section of the Polymer article explains the conventions used in naming polymers. copy link
Diagram This diagram from the Polymerization article illustrates some of the different shapes of polymeric molecules. Polymers are represented as long lines. copy link
Diagram When polymerizing asymmetric monosubstituted olefins, each monomer has two distinct ends, and can lead to three different regiochemistries in the polymer chain. This diagram from the Polymerization article illustrates these orientations. copy link
Diagram Three different stereochemical relationships can occur between groups attached to the main chain of a polymer. This diagram from the Polymerization article illustrates these three relationships. copy link
Diagram This diagram from the Polymer article illustrates the difference between linear and branched polymers using Lewis structures for polypropylene. copy link
Article Section Polymer properties depend heavily on the size of polymer chains and the interactions that the chains have with each other. The section on molecular properties in the Polymer article discusses these principles. copy link
Article Section This section on polymer size, from the Polymerization article, further discusses the relationship between size and properties of polymers. It includes the equation for calculating the polydisperity index (PDI), which quantifies the distribution of molecular weights among different polymer chains. copy link
Biography This biography of Hermann Staudinger describes his work demonstrating that polymers are large, covalently linked molecules. Staudinger received the Nobel Prize in Chemistry for this work in 1953. copy link
Diagram This diagram from a Research Review on polymer recycling and degradation shows Lewis structures for a number of common polymers. copy link
Radical-Chain Polymerization (Addition Polymerization)
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Reactions Reactions (6)–(10) in the Polymerization article illustrate the three fundamental reaction types (initiation, propagation, and termination) involved in a free-radical catalyzed polymerization. copy link
Diagram This figure from the Controlled/living radical polymerization article provides a mechanism for free-radical polymerization, including side reactions (i.e., recombination and disproportionation) that lead to uncontrolled polymer chain growth. copy link
Diagram This figure from Controlled/living radical polymerization illustrates active and dormant radical equilibrium. By keeping the radical mostly in a dormant state, undesirable side reactions are avoided. copy link
Diagram This third figure from Controlled/living radical polymerization illustrates the use of nitroxides as a dormant form of radical in nitroxide-mediated radical polymerization (NMRP). copy link
Diagram This fourth figure from Controlled/living radical polymerization shows the use of organic halides as a dormant form of radical in atom transfer radical polymerization (ATRP). During the polymerization process, the halide is reversibly transferred to a transition-metal catalyst, generating a radical. copy link
Diagram This fifth and last figure from Controlled/living radical polymerization shows the use of thiocarbonylthio compounds as a dormant form of radical in reversible addition-fragmentation transfer (RAFT) polymerization. copy link
Ionic and Complex Coordination Polymerization (Addition Polymerization)
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Reaction The Polymerization article exemplifies a cationic polymerization using a Lewis-acid catalyst in this reaction (12). copy link
Reaction This reaction (13) from the Polymerization article illustrates an anionic polymerization using n-butyllithium as the initiator. copy link
Animation This animation shows an example of anionic polymerization using ethylene. copy link
Reactions These two reactions [(14) and (15)] from the Polymerization article exemplify heterogeneous polymerization. copy link
Biography This biography of Karl Ziegler describes his contributions to the development of heterogeneous polymer catalysis, for which he shared a Nobel Prize in Chemistry with Giulio Natta (see below). copy link
Biography This biography of describes the contributions of Giulio Natta to the development of heterogeneous polymer catalysis, for which he shared a Nobel Prize in Chemistry with Karl Ziegler (see above). copy link
Diagram This diagram from the Single-site catalysts article illustrates the structures of several metallocene catalysts. These soluble catalysts complement the heterogeneous catalysts developed by Ziegler and Natta (see above biographies). copy link
Table The Single-site catalysts article includes this table comparing polypropylenes made using Ziegler-Natta and metallocene catalysts. copy link
Condensation Polymerization (Step Polymerization)
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Diagram This schematic from the Polymerization article illustrates the process of condensation (step) polymerization. Here, a and b represent reactive end groups on each monomer, where a and b react together to form a covalent link between monomers. copy link
Reaction This reaction (1) from the Polymerization article depicts the condensation polymerization of an ab-type monomer (a monomer that can react with itself) to form a polyamide (nylon). copy link
Reaction This reaction (2), also from Polymerization, illustrates the condensation polymerization of an aa- and bb-type monomer (a monomer that cannot react with itself) to form a polyamide. Have students compare this reaction with the one above it, and discuss why a similar product would be obtained in both cases. copy link
Graph This graph from Polymerization demonstrates how the molecular weight (size) of growing polymer chains increases with the amount of monomer consumed (conversion). Point out that, while addition polymerizations (see above) grow rapidly with conversion, the nature of step polymerizations mean that polymers are only obtained at very high conversions. copy link
Reaction This reaction (3) from the Polymerization article shows how cross-linked polymers can be formed through condensation (step) polymerization mechanisms by using monomers with more than two reactive groups. copy link
Ring-Opening Polymerization
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Reactions This set of reactions [(1)–(3)] from the article on ring-opening polymerization exemplify how anionic polymer end groups grow by reaction with (opening) cyclic monomers. copy link
Reaction This reaction (2) from the Ring-opening polymerization article shows how metals can be used to coordinate a growing polymer and cyclic monomer to facilitate polymerization. copy link
Research Review This article summarizes the area of ring-opening metathesis polymerization (ROMP), a relatively new polymerization method based on the exchange of double bonds in strained rings. This approach is an extension of the work that received the 2005 Nobel Prize in Chemistry (see the Biographies below). copy link
Biography This brief biography presents the life and work of Robert Grubbs, an American chemist who shared a Nobel Prize in Chemistry with Yves Chauvin and Richard Schrock for the development of catalysts for metathesis reactions. copy link
Biography The life and work of French chemist Yves Chauvin (see above) is briefly discussed in this biography. copy link
Biography This biography presents the third co-winner of the 2005 Nobel Prize in Chemistry, Richard Schrock, who developed the first efficient metal compound catalyst for the metathesis method as described by Chauvin (see above). copy link
Copolymers
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Diagram This schematic from the Polymerization article illustrates the difference between homopolymers and several types of copolymers made up of two different monomers represented here as A and B. copy link
Article Section This section of the Copolymer article, entitled Statistical copolymers, discusses features of preparing a copolymer by the simultaneous polymerization of two different monomers. Point out that the morphology of the copolymer formed by this method will depend on the concentration of each monomer and each monomer's individual reactivity. copy link
Diagram This elegant diagram from the Copolymer article shows how a block copolymer containing a hydrophobic block and a hydrophilic block can spontaneously form a micelle. copy link
Diagram This diagram from Copolymer shows how a block copolymer containing rigid blocks and flexible blocks can be used as a thermoplastic elastomer. Point out that, traditionally, elastomers have had chemical bonds connecting polymer chains. The block copolymer illustrated here forms physical links between chains, and is therefore easier to process and reuse. copy link
Common Synthetic Polymers
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Table This table from the Polymer article lists common polymers prepared annually in the United States. An interesting student exercise would be to compare these amounts with polymers synthesized in Europe and other parts of the world. copy link
Table This table from the Polymer article presents industrially important synthetic fibers, including their definitions and uses. copy link
Table This table, also from the Polymer article, lists important synthetic elastomers and their uses. copy link
Table This Polymer-article table lists important plastics and their uses. copy link
Naturally Occurring Polymers
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Article Section This first section of the Biopolymer article describes polypeptides—polyamides derived from amino acids. Students should understand that polypeptides form the basic structure of proteins. copy link
Article Section This second section of the Biopolymer article describes how sugars are connected to form polysaccharides. copy link
Article Section This last section of the Biopolymer article describes polyisoprenes—natural rubbers that are mostly polymers of isoprene. copy link
Diagram This diagram from the article on DNA illustrates the polymeric nature of deoxyribonucleic acid, the carrier of genetic information in living organisms. copy link
Animation This short and colorful animation helps illustrate the polymeric structure of DNA. copy link
Animation This animation helps illustrate the polymeric structure of proteins (polypeptides). The Flash®
 version of this animation is interactive, so students can proceed through each screen at their own pace.
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Green Polymer Chemistry
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Diagram This simple diagram from the Research Review on polymer recycling and degradation presents strategies for waste management, ranging from reduction of use to disposal in landfills. copy link
Diagram This diagram from Polymer recycling and degradation classifies polymers based on their source and biodegradability. copy link
Diagram This diagram from Polymer recycling and degradation illustrates some degradation mechanisms for a number of common polymer types. copy link
Article Section This brief section of the Research Review on polymers from renewable resources is a good introduction to the concept of polymeric materials made from vegetable oils. copy link
Article Section This brief section of the Polymers from renewable resources article can serve as an introduction to the concept of polymeric materials made from sugars. copy link
Article Section This brief section of Polymers from renewable resources introduces students to the concept of polymeric materials made from the resin of coniferous trees. copy link
Inorganic and Organometallic Polymers
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Diagram This diagram from the Inorganic and organometallic polymers article presents several structural examples of these types of polymers. copy link
Reaction This reaction from the article on inorganic and organometallic polymers exemplifies the formation of an inorganic polymer by a step-growth mechanism. Specifically, dihydroxymetallophthaloxyanine is polymerized through the loss of water to generate a so-called shish-kebab polymer. copy link
Table This table from Inorganic and organometallic polymers lists several cyclic monomers and the inorganic/organometallic polymers that they form by ring-opening polymerization. copy link
Diagram This diagram, also from Inorganic and organometallic polymers, illustrates the chain-growth mechanism of free-radical and electrochemical polymerizations forming organometallic polymers. copy link
Conducting Polymers
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Article Section Most polymers are electrically insulating, although there are exceptions. This section of the Organic conductor article serves as a good introduction to the topic of conducting polymers. copy link
Article Section This section of the Research Review on Nobel Prizes for 2000 summarizes the research on conducting polymers that received the prize in chemistry that year. copy link
Biography This brief biography of the U.S. physicist Alan Heeger describes his contributions to the development of conducting polymers, for which he shared the 2000 Nobel Prize in Chemistry with Alan Graham MacDiarmid and Hideki Shirakawa (see above article section). copy link
Biography U.S. chemist and Nobel-Prize winner Alan Graham MacDiarmid contributed to the development of conducting polymers (see above article section), as this brief biography discusses. copy link
Biography This brief biography of the Japanese chemist Hideki Shirakawa describes his contributions to the development of conducting polymers, for which he shared the 2000 Nobel Prize in Chemistry (see above article section). copy link
Applications
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Research Review Click chemistry in polymer science is a Research Review that describes how click chemistry is useful for making well-defined polymeric structures. Have students form conclusions from this article, which may include the fact that click chemistry involves reactions that are easy to perform, give complete conversion to products, and do not produce difficult-to-remove by-products. copy link
Diagram This diagram from the Research Review entitled Biological-synthetic hybrid polymers illustrates two cases where poly(ethylene glycol), or PEG, is attached to proteins using click reactions. Point out that the attachment of PEG allows therapeutic proteins—i.e., drugs—to stay in the bloodstream longer by masking the protein from the body's immune system. copy link
Briefing This Briefing describes research presented in a 2014 paper published in the Journal of the American Chemical Society, in which a polymer is prepared that mimics the protein lubricin. Lubricin is important for lubrication in joints, and a synthetic equivalent could be valuable to extending the lifetime of artificial joints. copy link
Diagram This full-color illustration from the Research Review on stimuli-responsive polymers demonstrates different ways that polymers can respond to stimuli such as temperature, light, mechanical stress, and pH changes. copy link
Diagram This diagram from the Research Review on shape-memory polymers illustrates a molecular process by which a polymer can physically move in response to specific stimuli—in this case, temperature. copy link
Diagram The Research Review on self-healing polymers includes this full-color illustration showing how, by embedding healing agents into a polymer, the polymer can repair cracks in itself without any human intervention. copy link
Diagram This diagram from the Self-healing polymers Research Review illustrates how polymers can repair themselves by incorporating dynamic covalent bonds, which are then able to break and reform under specific conditions, allowing the polymer to heal. copy link